2,4-dinitro- or 2-amino-4-nitro- or 2-nitro-4-amino-6-hydroxyalkylanilines, the process for preparation thereof and their use in dyeing keratinous fibers, and especially human hair

ABSTRACT

The invention relates to a compound of formula ##STR1## in which: X denotes a branched or unbranched alkylene radical containing 2 to 6 carbon atoms, optionally being able to be substituted with one or more hydroxyl radicals; 
     R denotes a hydrogen atom, an alkyl or a mono- or polyhydroxyalkyl radical or an aminoalkyl radical in which the amine group can be mono- or disubstituted with an alkyl radical or with a mono- or polyhydroxyalkyl radical, the nitrogen atom also being able to form part of a heterocyclic system and the alkyl radicals containing 1 to 4 carbon atoms; 
     R&#39; denotes a hydrogen atom or a C 1  to C 4  alkyl radical; 
     Y and Z denote a nitro and/or --NHR 1  radical, R 1  and R, which may be identical or different, having the meanings given above for R, with the proviso that when Y and Z are identical, they necessarily denote nitro radicals, 
     and the cosmetically acceptable salts of the compounds containing a salifiable amine group, and also the process for preparing it and its use in dyeing keratinous fibres, and especially human hair.

The present invention relates to new 2,4-dinitro- or 2-amino-4-nitro- or2-nitro-4-amino-6-hydroxyalkylanilines, the process for preparationthereof and their use in dyeing keratinous fibres, and especially humanhair, both by direct dyeing and by so-called oxidation dyeing.

It is well known that, to perform direct dyeing on hair or endow thelatter with complementary glints in the case of oxidation dyeing, nitroderivatives of the benzene series can be used.

The use has already been recommended, both in direct dyeing and inoxidation dyeing, of N-substituted 2,4-dinitroanilines, which areobtained by reaction of a primary amine with 2,4-dinitro-1-chlorobenzeneand also of nitro-orthophenylenediamines such as, more especially,2-amino-4-nitro-6-alkyl-anilines or nitro-paraphenylenediamines in whichthe nitrogen atoms are mono- or disubstituted.

Nevertheless, said compounds when used as direct dyes for dyeingkeratinous fibres, and more especially human hair, give rise to shadeswhich are insufficiently stable to light, adverse weather conditions orwashing.

Consequently, the Applicant has sought other nitroaminobenzene dyeswhich enable shades to be obtained which are more resistant to light,adverse weather conditions and washing, and has consequently discoveredthe compounds of formula: ##STR2## in which X denotes a branched orunbranched alkylene radical containing 2 to 6 carbon atoms, optionallybeing able to be substituted with one or more hydroxyl radicals;

R denotes a hydrogen atom, an alkyl or a mono- or polyhydroxyalkylradical or an aminoalkyl radical in which the amine group can be mono-or disubstituted with an alkyl or a mono- or polyhydroxyalkyl radical,the nitrogen atom also being able to form part of a heterocyclic system,and the alkyl radical containing 1 to 4 carbon atoms;

R' denotes a hydrogen atom or a C₁ to C₄ alkyl radical;

Y and Z denote a nitro and/or NHR₁ radical, R₁ and R, which may beidentical or different, having the meanings given above for R, with theproviso that when Y and Z are identical, they necessarily denote nitroradicals.

The subject of the present invention is hence the new2,4-dinitro-6-hydroxyalkylanilines of formula (Ia) ##STR3## the new2-amino-4-nitro-6-hydroxyalkylanilines of formula (Id) ##STR4## and thenew 2-nitro-4-amino-6-hydroxyalkylanilines of formula (Ie) ##STR5## R',X, R and R₁ having the meanings given above, as well as the cosmeticallyacceptable salts of the compounds (Ia), (Id) and (Ie) containing onesalifiable amine group.

By way of preferred radicals x, ethylene, propylene,1,1-dimethylethylene, 1,2-dimethylethylene and 1,1,2-trimethylethyleneradicals may be mentioned.

By way of preferred radicals R and R₁, hydrogen and methyl, ethyl,n-propyl, β-hydroxyethyl, γ-hydroxypropyl, β, γ-dihydroxypropyl,β-aminoethyl and β-diethylaminoethyl radicals may be mentioned.

By way of preferred radicals R', hydrogen and the methyl radical may bementioned.

Preferred compounds of formula (Ia) according to the invention are thefollowing:

2-(2-amino-3,5-dinitrophenyl)ethanol;

2-[2-(β-hydroxyethyl)amino-3,5-dinitrophenyl]ethanol;

1-(2-amino-3,5-dinitrophenyl)-2-propanol;

1-(2-methylamino-3,5-dinitrophenyl)-2-propanol;

1-[2-(β-aminoethyl)amino-3,5-dinitrophenyl]-2-propanol,

as well as the salts thereof.

Preferred compounds of formula (Id) according to the invention are thefollowing:

2-(2,3-diamino-5-nitrophenyl)ethanol;

2-[3-amino-2-(β-hydroxyethyl)amino-5-nitrophenyl]ethanol;

1-(2,3-diamino-5-nitrophenyl)-2-propanol;

1-(3-amino-2-methylamino-5-nitrophenyl)-2-propanol,

as well as the salts thereof.

Preferred compounds of formula (Ie) according to the invention are thefollowing:

2-(2,5-diamino-3-nitrophenyl)ethanol;

1-(2,5-diamion-3-nitrophenyl)-2-propanol;

1-[2-amino-5-(β-hydroxyethyl)amino-3-nitrophenyl]-2-propanol,

as well as the salts thereof.

The subject of the invention is also the process for preparing thecompounds of formula (I), which consists in reacting an aqueous ammoniasolution or a primary aliphatic amine R--NH₂, where R has the meaninggiven above, with the heterocyclic compounds of formula (II), accordingto the following reaction scheme: ##STR6## R' and X having the meaninggiven above to obtain a 2,4-dinitro-6-hydroxyalkylaniline of formula(Ia) which is then optionally subjected to a selective reduction toobtain a 2-amino-4-nitro-6-hydroxyalkylaniline of formula (Ib) or a2-nitro-4-amino-6-hydroxyalkylaniline of formula (Ic), which are thenoptionally subjected to an alkylation, a hydroxyalkylation or anaminoalkylation according to a conventional chemical process, to obtainthe final compound of formula (Id) and (Ie) respectively. To obtain thecompound of formula (Ic), selective reduction is performed on thecompound (Ia) in which R=H, which is obtained by reacting aqueousammonia solution with the heterocyclic compound (II).

The scheme for the process is as follows: ##STR7## R', X and R₁ havingthe meaning given above.

The opening of the heterocyclic ring by the primary amine or by ammoniais performed at a temperature between 20° and 120° C., optionally underpressure, in the presence or absence of polar protic solvents such aswater, alcohols, glycols or glycol ethers, or polar aprotic solventssuch as formamide, dimethylformamide, dioxane or tetrahydrofuran.

The compounds of formula (II) are obtained by nitration of the compoundsof formula (III): ##STR8## where R' and X have the meaning given above,the nitration being performed by adding the compound (III) to fumingnitric acid at a temperature between 30° and 35° C. [according to G.CHATELUS--Ann. Chem. 4, 505-547 (1949)] or by adding the compound (III)to a mixture of concentrated sulphuric and nitric acids at a temperaturein the region of 5° C. [according to Charles D. HURD, RostyslawDOWBENKO, J.A.C.S. 80, 4711-14 (1958)]; the compound (II) is thenisolated after dilution of the reaction medium with water.

Compounds of formula (III) are known, and most of the compounds offormula (II) are also known.

Among the known compounds of formula (II), the following may bementioned: 5,7-dinitrocoumaran (or 2,3-dihydro-5,7-dinitrobenzofuran),2-methyl-5,7-dinitrocoumaran, 2,2-dimethyl-5,7-dinitrocoumaran,2,3-dimethyl-5,7-dinitrocoumaran and2,2,3-trimethyl-5,7-dinitrocoumaran.

The selective reduction of the compound of formula (Ia) to obtain thecompound (Ib) is performed either with a hydroalcoholic solution ofsodium sulphide in the presence of sulphur at a temperature between 10°and 70° C., or with hydrogen sulphide in the presence of ammoniasolution according to M. KAMEL, M. I. ALI and M. M. KAMEL, TETRAHEDRON1966, vol. 22, p. 3353, or alternatively by transfer of hydrogen fromcyclohexene to the compound (Ia) in the presence of Pd/C, in C₁ -C₄lower alcohols and at a temperature between 15° C. and the boilingpoint, in a manner similar to that of Ian D. ENTWISTLE, Robert A. W.JOHNSTENE and Jeffery POVALL [(J. C. S. PERKIN I (1975), p. 1300].

The selective reduction of the compound of formula (Ia) in which R=H toobtain the compound (Ic) is performed by transfer of hydrogen fromcyclohexene to the compound (Ia), Pd/C being used as catalyst, in thepresence of alcohol, water and an inorganic acid such as concentratedhydrochloric acid.

The compounds (Ic) can also be obtained by selective reduction of thecompounds (Ia) in which R=H in a polar solvent such as a C₁ -C₅ alcohol,by introduction of hydrogen in the presence of a hydrogenation catalystsuch as Pd/C and an aqueous solution of an inorganic acid such as HCl,H₂ SO₄ or H₃ PO₄, at a temperature between 20° and 90° C. This processis described in French Pat. No. 1,303,215.

The conventional processes of alkylation, hydroxyalkylation oraminoalkylation used to obtain the compounds of formulae (Id) and (Ie)from compounds (Ib) and (Ic) can, for example, be those described inFrench Pat. Nos. 2,348,911, 2,497,662 and 2,492,370 of the Applicant, orother conventional processes.

The process for preparing the compounds of formula (I) according to theinvention enable excellent yields of these compounds to be obtained.

A further subject of the present invention consists of a dyeingcomposition for keratinous fibres, and more especially for human hair,containing at least one 2,4-dinitro- or one 2-amono-4-nitro- or one2-nitro-4-amino-6-hydroxyalkylaniline of formula (Ia), (Id) or (Ie)above, or one of its cosmetically acceptable salts, in a solvent medium.

The present invention also relates to a process for dyeing keratinousfibres, and more especially human hair, by direct dyeing or by oxidationdyeing involving development with an oxidising agent.

The dyeing compositions according to the invention contain, in a solventmedium, at least one compound corresponding to the formula (I), or oneof its cosmetically acceptable salts, and can be used for direct dyeingof keratinous fibres or for oxidation dyeing of these fibres, in whichcase the compounds of formula (I) confer glints which are complementaryto the basic coloration obtained by oxidative development of precursorsof oxidation dyes.

These compositions contain the compounds according to the invention inproportions of between 0.001 and 5% by weight, and preferably between0.05 and 2% by weight, relative to the total weight of the composition.

The solvent medium is preferably a cosmetic vehicle generally consistingof water, but organic solvents can also be added into the compositionsto solubilise compounds which would not be sufficiently soluble inwater. Among these solvents, there may be mentioned lower alkanols suchas ethanol and isopropanol, aromatic alcohols such as benzyl alcohol,polyols such as glycerol, glycols or glycol ethers such as2-butoxyethanol or 2-ethoxyethanol, ethylene glycol and propyleneglycol, diethylene glycol monomethyl ether and monoethyl ether and alsosimilar products and mixtures thereof. These solvents are preferablypresent in proportions ranging from 1 to 75% by weight, and especiallyfrom 5 to 50% by weight, relative to the total weight of thecomposition.

These compositions can contain anionic, cationic, nonionic or amphotericsurfactants, or mixtures thereof. These surfactants are present in thecompositions of the invention in proportions of between 0.5 and 55% byweight, and preferably between 4 and 40% by weight, relative to thetotal weight of the composition.

The compositions can be thickened, preferably with compounds chosen fromsodium alginate, gum arabic, cellulose derivatives such asmethylcellulose, hydroxyethylcellulose, hydroxypropylmethylcellulose andcarboxymethylcellulose and various polymers which have the function of athickener such as, more especially, acrylic acid derivatives. It is alsopossible to use inorganic thickening agents such as bentonite. Thesethickening agents are preferably present in proportions of between 0.5and 10% by weight, and especially between 0.5 and 2% by weight, relativeto the total weight of the composition.

The compositions according to the invention can also contain variousadjuvants customarily used in dyeing compositions for the hair, andespecially penetrants, dispersants, sequestering agents, film-formingagents, buffers and perfumes.

These compositions can take various forms such as liquid, cream or gelform, or any other form suitable for carrying out hair dyeing. They canin addition be packaged in aerosol containers in the presence of apropellant.

The pH of these dyeing compositions can be between 3 and 11.5, andpreferably between 5 and 11.5. It is adjusted to the desired value usingan alkalinising agent such as ammonia solution, sodium carbonate,potassium carbonate or ammonium carbonate, sodium hydroxide or potassiumhydroxide, alkanolamines such as mono-, di- or triethanolamine,2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, oralkylamines such as ethylamine or triethylamine, or using an acidifyingagent such as phosphoric, hydrochloric, tartaric, acetic, lactic orcitric acid.

When the compositions are intended for use in a process for directdyeing of hair, they can contain, in addition to the compounds accordingto the invention, other direct dyes such as azo or anthraquinone dyes,for example 1,4,5,8-tetraaminoanthraquinone, indophenols, indoanilinesand nitro dyes of the benzene series other than the compounds of formula(I).

The concentrations of these direct dyes other than the dyes of formula(I) can be between 0.001 and 5% by weight relative to the total weightof the composition.

These compositions, employed in a direct dyeing process, are applied onthe keratinous fibres for an exposure time which varies from 5 to 50minutes, the fibres are then rinsed, optionally washed with shampoo,rinsed again and dried.

The compositions according to the invention can also be employed in theform of hair setting lotions intended at one and the same time to endowthe hair with a light coloration or with glints, and to improve theshaperetention of the set. In this case, they take the form of aqueous,alcoholic or hydroalcoholic solutions containing at least one cosmeticresin, and they are applied on damp hair which has been washed andrinsed beforehand and which is optionally coiled and then dried.

The cosmetic resins which are used in the setting lotions can be, inparticular, polyvinylpyrrolidone, crotonic acid/vinyl acetate,vinylpyrrolidone/vinyl acetate, maleic anhydride/butyl vinyl ether andmaleic anhydride/methyl vinyl ether copolymers, as well as any othercationic, anionic, nonionic or amphoteric polymer customarily used inthis type of composition. These cosmetic resins participate in thecompositions of the invention in the proportion of 0.5 to 4% by weight,and preferably from 1 to 3% by weight, based on the total weight of thecomposition.

When the compositions according to the invention constitute oxidationdyes, involving development with an oxidising agent, the compounds offormula (I) according to the invention are mainly used for the purposeof contributing glints to the final dyeing.

These compositions then contain, in combination with at least one nitrodye of formula (I) and optionally other direct dyes, oxidation dyeprecursors.

The compositions can contain, for example, paraphenylenediamines suchas: para-phenylenediamine, paratolylenediamine,2-chloro-para-phenylenediamine, 2,6-dimethyl-para-phenylenediamine,2,6-dimethyl-3-methoxy-paraphenylenediamine,N-(β-methoxyethyl)-para-phenylenediamine,N,N-bis(≢-hydroxyethyl)-para-phenylenediamine,4-[N-ethyl-N-(carbamylmethyl)amino]aniline and also the salts thereof.

They can also contain para-aminophenols, for example: para-aminophenol,N-methyl-para-aminophenol, 2-chloro-4-aminophenol,3-chloro-4-aminophenol, 2-methyl-4-aminophenol and the salts thereof.

They can also contain ortho-aminophenol.

They can also contain heterocyclic derivatives, for example:2,5-diaminopyridine and 7-aminobenzomorpholine.

The compositions according to the invention can contain, in combinationwith the oxidation dye precursors, couplers which are well-known in thestate of the art.

By way of couplers, there may be mentioned, in particular:meta-diphenols, meta-aminophenols and the salts thereof,meta-phenylenediamines and the salts thereof, meta-acylaminophenols,meta-ureidophenols and meta-carbalkoxyaminophenols.

As other couplers which can be used in the compositions according to theinvention, there may finally be mentioned: α-naphthol, couplerspossessing an active methylene group such as diketo compounds andpyrazolones, and heterocyclic couplers derived from pyridine andbenzomorpholine.

These compositions contain, in addition to the oxidation dye precursors,reducing agents present in proportions of between 0.05 and 3% by weightrelative to the total weight of the composition.

The oxidation dye precursors can be used, in the compositions of theinvention, at concentrations of between 0.001 and 5% by weight, andpreferably between 0.03 and 2% by weight, based on the total weight ofthe composition. The couplers can also be present in proportions ofbetween 0.001 and 5% by weight, and preferably between 0.015 and 2% byweight. The pH of these oxidation dyeing compositions is preferablybetween 7 and 11.5, and is adjusted using alkalinising agents definedabove.

The process of dyeing the keratinous fibres, especially human hair,employing development by an oxidising agent, consists in applying on thehair the dyeing composition containing both a dye according to theinvention and dye precursors. The development of the coloration can thenbe accomplished slowly in the presence of the oxygen in the air, but achemical development system is preferably used, this most frequentlybeing chosen from hydrogen peroxide, urea peroxide and persalts. Asolution of "20 volumes" hydrogen peroxide is used in particular.

When the composition with the oxidising agent has been applied on thekeratinous fibres, it is left in place for 10 to 50 minutes, preferably15 to 30 minutes, after which the keratinous fibres are rinsed,optionally washed with shampoo, rinsed again and dried.

The examples which follow are intended to illustrate the inventionwithout being limitative in nature.

PREPARATION EXAMPLE 1 ##STR9## Preparation of2-(2-amino-3,5-dinitrophenyl)ethanol

0.17 Mole (35.7 g) of 2,3-dihydro-5,7-dinitrobenzofuran, preparedaccording to Chatelus Ann. Chim. [12], 4,505-547 (1949), is suspended in350 ml of 20% strength ammonia solution and 220 ml of formamide. After 8hours' heating at 110° C., a further 100 ml of 20% strength ammoniasolution are added. Heating is maintained for 4 hours. When the reactionmedium is cooled, the expected product precipitates.

After being drained, washed with ice-cold water until neutral and driedunder vacuum, 0.13 mole (30.3 g) of a product melting at 151° C. isobtained, and this is recrystallized from dioxane.

Analysis of the product gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.8 H.sub.9 N.sub.3 O.sub.5                                                           Found                                               ______________________________________                                        % C           42.29       42.24                                               % H            3.99        3.91                                               % N           18.50       18.60                                               % O           35.21       35.14                                               ______________________________________                                    

PREPARATION EXAMPLE 2 ##STR10## Preparation of2-[2-(β-hydroxyethyl)amino-3,5-dinitrophenyl]ethanol

0.29 Mole (60.9 g) of 2,3-dihydro-5,7-dinitrobenzofuran is added insmall portions at room temperature to 122 ml of 2-aminoethanol. Afterthe addition is complete, the reaction medium is brought for 15 minutesto 95° C. 500 ml of water are added; after the mixture is cooled, theexpected product is drained, and this, after being made into a paste inwater and recrystallized from 75 ml of 96° strength ethanol, melts at115° C.

Analysis gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.10 H.sub.13 N.sub.3 O.sub.6                                                         Found                                               ______________________________________                                        % C           44.28       44.38                                               % H            4.83        4.74                                               % N           15.49       15.48                                               % O           35.39       35.60                                               ______________________________________                                    

PREPARATION EXAMPLE 3 ##STR11## Preparation of1-(2-amino-3,5-dinitrophenyl)-2-propanol

0.39 Mole (88 g) of 2,3-dihydro-5,7-dinitro-2-methylbenzofuran, preparedaccording to J.A.C.S. 80, p. 4711-4714 (1958), is suspended in 1.1 l of20% strength ammonia solution and 600 ml of Methyl Cellosolve. After 18hours' heating at 70° C., the reaction mixture is cooled. Theprecipitate formed is drained and, after being made into a paste inwater until neutral and then dried under vacuum, is recrystallized from170 ml of dioxane. After being dried under vacuum, 0.30 mole (72 g) ofthe expected product is obtained; it melts at 177° C.

Analysis gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.9 H.sub.11 N.sub.3 O.sub.5                                                          Found                                               ______________________________________                                        % C           44.81       44.87                                               % H            4.60        4.62                                               % N           17.42       17.45                                               % O           33.17       33.08                                               ______________________________________                                    

PREPARATION EXAMPLE 4 ##STR12## Preparation of1-(2-methylamino-3,5-dinitrophenyl)-2-propanol

0.056 Mole (12.5 g) of 2,3-dihydro-5,7-dinitro-2-methyl-benzofuran issuspended in 100 ml of a 33% strength solution of methylamine inethanol. After 10 hours' stirring at room temperature in a sealedErlenmeyer, the reaction mixture is brought for 30 minutes to therefluxing temperature of the alcohol. After the mixture is cooled, theexpected product precipitates. It is drained, washed with alcohol andthen recrystallized from 50 ml of 96° strength ethanol. After beingdried, 0.047 mole (12 g) is obtained of a product which melts at 132° C.

Analysis gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.10 H.sub.13 N.sub.3 O.sub.5                                                         Found                                               ______________________________________                                        % C           47.06       47.11                                               % H            5.13        5.03                                               % N           16.47       16.52                                               % O           31.34       31.25                                               ______________________________________                                    

PREPARATION EXAMPLE 5 ##STR13## Preparation of1-[2-(β-aminoethyl)amino-3,5-dinitrophenyl]-2-propanol

0.089 Mole (20 g) of 2,3-dihydro-5,7-dinitro-2-methylbenzofuran is addedwith stirring at room temperature to 40 ml of ethylenediamine. When theaddition is complete, the reaction medium is poured into 500 ml ofwater. The expected product precipitates. After being drained and madeinto a paste in water, it is recrystallized from 210 ml of 96° strengthethanol. 0.074 mole (20.9 g of a product is obtained which melts at 140°C.

Molecular mass calculated for C₁₁ H₁₆ N₄ O₅ : 284.

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 293.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.11 H.sub.16 N.sub.4 O.sub.5                                                         Found                                               ______________________________________                                        % C           46.47       46.40                                               % H            5.67        5.68                                               % N           19.71       19.82                                               % O           28.14       27.95                                               ______________________________________                                    

PREPARATION EXAMPLE 6 Preparation of2-(2,3-diamino-5-nitrophenyl)ethanol ##STR14##

To a suspension of 0.119 mole (27 g) of2-(2-amino-3,5-dinitrophenyl)ethanol obtained in Example 1 in 67.5 ml ofisopropanol to which an equal volume of water has been added, asolutionof 38.4 g of sodium sulphide nonahydrate and 5.4 g of sulphur in10 ml of water is added dropwise at 60°-65° C. Heating is maintained for20 minutes after the addition is complete. When the mixture is cooled, aprecipitate of the expected product is obtained, and this is drained,made into a paste in water and then recrystallized from 96° strengthalcohol. It melts at 172° C.

Molecular mass calculated for C₈ H₁₁ N₃ O₃ : 197

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 202.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.8 H.sub.11 N.sub.3 O.sub.3                                                          Found                                               ______________________________________                                        % C           48.72       48.84                                               % H            5.62        5.71                                               % N           21.31       21.40                                               % O           24.34       24.30                                               ______________________________________                                    

PREPARATION EXAMPLE 7 Preparation of2-[3-amino-2-(β-hydroxyethyl)amino-5-nitrophenyl]ethanol ##STR15##

After 0.14 mole (38 g) of2-[2-(β-hydroxyethyl)amino-3,5-dinitrophenyl]ethanol, obtained inExample 2, has been added to 530 ml of absolute alcohol to which 56 mlof 20% strength ammonia solution have been added, hydrogen sulphide isbubbled into this alcoholic solution for 2 hours; the temperature risesto 27° C. The bubbling is then stopped. The reaction medium is broughtto reflux for 4 hours and then left for 48 hours at room temperature.After concentration of the alcoholic solution to one half, the inorganicsalts are filtered off. The filtrate is then evaporated to dryness. Thedry residue is made into a paste in isopropanol. After recrystallizationin order to remove a resin, the produce melts at 121° C.

Molecular mass calculated for C₁₀ H₁₅ N₃ O₄ : 241

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 247

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.10 H.sub.15 N.sub.3 O.sub.4                                                         Found                                               ______________________________________                                        % C           49.78       49.87                                               % H            6.27        6.27                                               % N           17.42       17.38                                               % O           26.53       26.25                                               ______________________________________                                    

PREPARATION EXAMPLE 8 Preparation of1-(2,3-diamino-5-nitrophenyl)-2-propanol ##STR16##

To a suspension of 0.1 mole (24.1 g) of1-(2-amino-3,5-dinitrophenyl)-2-propanol, obtained in Example 3, in 60ml of isopropanol to which an equal volume of water has been added, asolution of 33.6 g of sodium sulphide nonahydrate and 4.8 g of sulphurin 9 ml of water is added dropwise at 60° C.

Heating is maintained for 20 minutes after the addition is complete.When the mixture is cooled, the expected product is obtained, and thisis drained, made into a paste in water and recrystallized in 96°strength ethanol. It melts at 174° C.

Molecular mass calculated for C₉ H₁₃ N₃ O₃ : 211

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 216.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.9 H.sub.13 N.sub.3 O.sub.3                                                          Found                                               ______________________________________                                        % C           51.17       51.09                                               % H            6.20        6.19                                               % N           19.90       20.13                                               % O           22.73       22.57                                               ______________________________________                                    

PREPARATION EXAMPLE 9 Preparation of1-(3-amino-2-methylamino-5-nitrophenyl)-2-propanol monohydrochloride##STR17##

After 0.027 mole (6.88 g) of1-(2-methylamino-3,5-dinitrophenyl)-2-propanol, obtained in Example 4,has been added to 100 ml of absolute ethanol to which 10.8 ml of 20%strength ammonia solution have been added, hydrogen sulphide is bubbledinto the mixture for 2 h 30 min. After 1 hour, the temperature rises to35° C. and then drops again. After the alcoholic solution isconcentrated to one half, the inorganic salts are filtered off. Thefiltrate is evaporated to dryness; the dry extract in oily form is takenup with a solution of hydrochloric acid in absolute ethanol. On dilutionwith ethyl ether, the monohydrochloride of the expected product isobtained, and this is recrystallized from a hydroalcoholic mixture.

Molecular mass calculated for C₁₀ H₁₆ N₃ O₃ Cl: 261.

Molecular mass found by potentiometric assay in water using sodiumhydroxide: 264.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.10 H.sub.16 N.sub.3 O.sub.3 Cl                                                      Found                                               ______________________________________                                        % C           45.89       46.00                                               % H            6.12        6.13                                               % N           16.06       16.21                                               % O           18.35       18.38                                               % Cl          13.57       13.64                                               ______________________________________                                    

PREPARATION EXAMPLE 10 Preparation of2-(2,5-diamino-3-nitrophenyl)ethanol ##STR18##

To a suspension of 15.7 g of Pd/C (containing 10% Pd) in 290 ml ofabsolute ethanol to which 35 ml of concentrated hydrochloric acid and 64ml of cyclohexene have been added, 0.141 mole (32 g) of2-(2-amino-3,5-dinitrophenyl)ethanol, obtained according to Example 1,is added. After 1 h 45 min of heating under reflux, the reaction mediumis filtered hot to remove the catalyst. The filtrate is evaporated todryness under vacuum and the dry extract, after being washed withabsolute ethanol, is solubilised hot in water. 15 ml of 20% strengthammonia solution are added. When the mixture is cooled to a redprecipitate of the expected product is obtained, and this, after beingdrained is recrystallized from Methyl Cellosolve. After being dried, theproduct melts at 190° C.

Molecular mass calculated for C₈ H₁₁ N₃ O₃ : 197.

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 199.5.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.8 H.sub.11 N.sub.3 O.sub.3                                                          Found                                               ______________________________________                                        % C           48.72       48.88                                               % H            5.62        5.67                                               % N           21.31       21.33                                               % O           24.34       24.60                                               ______________________________________                                    

PREPARATION EXAMPLE 11 Preparation of1-(2,5-diamino-3-nitrophenyl)-2-propanol ##STR19##

To a suspension of 5.6 g of Pd/C (containing 10% Pd) in 100 ml ofabsolute ethanol to which 12.5 ml of concentrated hydrochloric acid and23 ml of cyclohexene have been added, 0.05 mole (12.05 g) of1-(2-amino-3,5-dinitrophenyl)-2-propanol, obtained according to Example3, is added. After 3 hours' heating under reflux, the reaction medium isfiltered hot to remove the catalyst. The filtrate is evaporated todryness, and the dry extract is made into a paste in an ethanol/ethylether mixture and then solubilised hot in the minimum of water. 15 ml of20% strength ammonia solution are added in order to displace thehydrochloride. The expected product precipitates. After being drained,washed with water and recrystallized from 96° strength ethanol, it meltsat 168° C.

Molecular mass calculated for C₉ H₁₃ N₃ O₃ : 211

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 210.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.9 H.sub.13 N.sub.3 O.sub.3                                                          Found                                               ______________________________________                                        % C           51.17       51.31                                               % H            6.20        6.21                                               % N           19.90       20.03                                               % O           22.73       22.66                                               ______________________________________                                    

PREPARATION EXAMPLE 12 Preparation of1-[2-amino-5-(β-hydroxyethyl)amino-3-nitrophenyl]-2-propanol ##STR20##1st stage Preparation ofβ-chloroethyl[4-amino-5-(β-hydroxypropyl)-3-nitrophenyl]carbamat

0.07 Mole (14.8 g) of 1-(2,5-diamino-3-nitrophenyl)-2-propanol, obtainedin Preparation Example 11, is dissolved in 59 ml of dioxane to which 22ml of water have been added. 0.0385 Mole (5.3 g) of potassium carbonateis added. The temperature is raised to 90° C., and then 0.077 mole (11g) β-chloroethyl chloroformate is then introduced in small portions withstirring. When the addition is complete, the reaction mixture is pouredonto 400 g of a water/ice mixture. The expected product precipitates;after being drained and dried under vacuum, 21.8 g of the expectedproduct are obtained. It melts at 115° C.

2nd stage

Preparation of N-[4-amino-5-(β-hydroxypropyl)-3-nitrophenyl]oxazolidone

0.056 Mole (17.8 g) of β-chloroethyl[4-amino-5-(62-hydroxypropyl)-3-nitrophenyl]carbamate is suspended in 107 ml of 96°strength alcohol. 12 ml of a solution of sodium methylate at 30%strength in methanol are added dropwise, the temperature beingmaintained at 10° C. After being drained and made into a paste in water,0.041 mole (11.6 g) of the expected product is obtained.

3rd stage

Preparation of1-[2-amino-5-(β-hydroxyethyl)amino-3-nitrophenyl]-2-propanol

0.041 Mole (11.5 g) ofN-[4-amino-5-(β-hydroxypropyl)-3-nitrophenyl]oxazolidone is introducedinto 46 ml of 96° strength alcohol. The temperature is raised to 85° C.and 8.2 ml of 10N sodium hydroxide solution is poured in dropwise.Heating is maintained for 15 minutes after the addition is complete.After filtration, the filtrate is evaporated to dryness and the residueis then taken up with 40 ml of water. The expected product crystallizes;after recrystallization from water, it melts at 130° C.

Molecular mass calculated for C₁₁ H₁₇ N₃ O₄ : 255

Molecular mass found by potentiometric assay in acetic acid usingperchloric acid: 256.

Analysis of the product obtained gives the following results:

    ______________________________________                                                      Calculated for                                                  Analysis      C.sub.11 H.sub.17 N.sub.3 O.sub.4                                                         Found                                               ______________________________________                                        % C           51.75       51.80                                               % H            6.71        6.70                                               % N           16.46       16.62                                               % O           25.07       25.18                                               ______________________________________                                    

EXAMPLE 1

The following dyeing composition is prepared:

    ______________________________________                                        2-(2-Amino-3,5-dinitrophenyl)ethanol                                                                     0.2    g                                           96° strength alcohol                                                                              15     g                                           ALFOL C.sub.16/18          8      g                                           Lanette Wax E              0.5    g                                           CEMULSOL B                 1      g                                           Oleic diethanolamide       1.5    g                                           Triethanolamine, 1% concentration by weight                                                              1      g                                           Water q.s.                 100    g                                           pH 8.4                                                                        ______________________________________                                    

When applied for 30 minutes at 28° C. on hair which has been bleachedwhite, this mixture endows it, after shampooing and rinsing, with acoloration 6.25 Y 8.5/6, according to Munsell's notation.

EXAMPLE 2

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-(β-Hydroxyethyl)amino-3,5-dinitro-                                                             0.36   g                                           phenyl]ethanol                                                                2-Butoxyethanol            10     g                                           ALFOL C.sub.16/18          8      g                                           Lanette Wax E              0.5    g                                           CEMULSOL B                 1      g                                           Oleic diethanolamide       1.5    g                                           Triethanolamine, 1% concentration by weight                                                              1      g                                           Water q.s.                 100    g                                           pH 7.8                                                                        ______________________________________                                    

When applied on hair for 20 minutes at 28° C., this mixture endows it,after shampooing and rinsing, with a coloration:

5 Y 8.5/7 on hair which has been bleached white;

5 y 8/5 on hair which is naturally 90% white, these colors beingexpressed according to Munsell's notation.

EXAMPLE 3

The following dyeing composition is prepared:

    ______________________________________                                        1-(2-Amino-3,5-dinitrophenyl)-2-propanol                                                                0.24   g                                            Propylene glycol          10     g                                            COMPERLAN KD              2.2    g                                            Lauric acid               0.8    g                                            2-Ethoxyethanol           2      g                                            Monoethanolamine          1      g                                            Water q.s.                100    g                                            pH 8.4                                                                        ______________________________________                                    

When applied for 30 minutes at 28° C. on hair which has been bleachedwhite, this mixture endows it, after shampooing and rinsing, with acoloration 3.75 Y 8.5/5 according to Munsell's notation.

EXAMPLE 4

The following dyeing composition is prepared:

    ______________________________________                                        1-(2-Methylamino-3,5-dinitrophenyl)-2-                                                                  0.36   g                                            propanol                                                                      96° strength alcohol                                                                             12     g                                            COMPERLAN KD              2.2    g                                            Lauric acid               0.8    g                                            2-Ethoxyethanol           2      g                                            Monoethanolamine          1      g                                            Water q.s.                100    g                                            pH 8                                                                          ______________________________________                                    

When applied for 20 minutes at 30° C. on hair which has been bleachedwhite, this mixture endows it, after shampooing and rinsing, with acoloration 7 Y 8.5/4 according to Munsell's notation.

EXAMPLE 5

The following dyeing composition is prepared:

    ______________________________________                                        1-[2-(β-Aminoethyl)amino-3,5-dinitro-                                                             0.12   g                                             phenyl]-2-propanol                                                            2-Butoxyethanol          8      g                                             CARBOPOL 934             2      g                                             2-Amino-2-methyl-1-propanol in 25%                                                                     2      g                                             strength solution in water                                                    Water q.s.               100    g                                             pH 5                                                                          ______________________________________                                    

When applied for 30 minutes at 30° C. on hair which has been bleachedwhite, this mixture endows it, after shampooing and rinsing, with acoloration 5 Y 8.5/7 according to Munsell's notation.

EXAMPLE 6

The following dyeing composition is prepared:

    ______________________________________                                        1-[2-(β-Aminoethyl)amino-3,5-dinitro-                                                              0.415  g                                            phenyl]-2-propanol                                                            3-Nitro-4-methylamino-N,N--bis(β-hydroxy-                                                          0.155  g                                            ethyl)aniline                                                                 2-Methyl-4-amino-3-nitro-N--(β-hydroxy-                                                            0.08   g                                            ethyl)aniline                                                                 96° strength alcohol                                                                             12     g                                            ALFOL C.sub.16/18         8      g                                            Lanette Wax E             0.5    g                                            CEMULSOL B                1      g                                            Oleic diethanolamide      1.5    g                                            Monoethanolamine in 20% strength solution                                                               0.25   g                                            in water                                                                      Water q.s.                100    g                                            pH 9.4                                                                        ______________________________________                                    

When applied for 20 minutes at 28° C. on bleached hair, this mixtureendows it, after shampooing and rinsing with a hazel coloration.

EXAMPLE 7

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-(β-hydroxyethyl)amino-3,5-                                                                    0.47   g                                            dinitrophenyl]ethanol                                                         3-Nitro-4-(β-hydroxyethyl)aminophenol                                                              0.13   g                                            1,4,5,8-Tetraaminoanthraquinone (Cibacete                                                               0.08   g                                            microdisperse blue)                                                           2-Butoxyethanol           10     g                                            CELLOSIZE WP 03           2      g                                            (Tallow alkyl)dimethylhydroxyethylammonium                                                              2      g                                            chloride                                                                      5% strength ammonia solution                                                                            0.15   g                                            Water q.s.                100    g                                            pH 8                                                                          ______________________________________                                    

When applied for 25 minutes at 28° C. on bleached hair, this mixtureendows it, after shampooing and rinsing, with a golden dark blondecoloration.

EXAMPLE 8

The following dyeing composition is prepared:

    ______________________________________                                        2-[2-(β-Hydroxyethyl)amino-3,5-dinitro-                                                            0.205  g                                            phenyl]ethanol                                                                Para-phenylenediamine     0.08   g                                            Para-aminophenol          0.06   g                                            Resorcinol                0.085  g                                            Meta-aminophenol          0.06   g                                            3-(β-Hydroxyethyl)amino-6-methylphenol                                                             0.05   g                                            Polyglycerolated oleic alcohol (2 moles                                                                 4.5    g                                            of glycerol)                                                                  Polyglycerolated oleic alcohol (4 moles of                                                              4.5    g                                            glycerol)                                                                     ETHOMEEN TO 12            4.5    g                                            COMPERLAN KD              9      g                                            Propylene glycol          4      g                                            2-Butoxyethanol           8      g                                            96° ethanol        6      g                                            MASQUOL DTPA              2      g                                            Thioglycolic acid         0.6    g                                            Ammonia solution, 22° Be                                                                         10     g                                            Water q.s.                100    g                                            pH 10.5                                                                       ______________________________________                                    

At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 25 minutes at 30° C. on bleached hair, the mixtureendows it, after shampooing and rinsing, with a golden chestnutcoloration.

EXAMPLE 9

The following dyeing composition is prepared:

    ______________________________________                                        2-(2,3-Diamino-5-nitrophenyl)ethanol                                                                     0.15   g                                           Propylene glycol           10     g                                           CEMULSOL NP 4              12     g                                           CEMULSOL NP 9              15     g                                           Polyglycerolated oleic alcohol (2 moles                                                                  1.5    g                                           of glycerol)                                                                  Polyglycerolated oleic alcohol (4 moles                                                                  1.5    g                                           of glycerol)                                                                  Monoethanolamine in a 20% strength solution                                                              1.5    g                                           in water                                                                      Water q.s.                 100    g                                           pH 10                                                                         ______________________________________                                    

When applied on hair for 20 minutes at 28° C., this mixture endows it,after shampooing and rinsing, with a coloration:

10 YR 7.5/8 on hair bleached white:

5 Y 8/6 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 10

The following dyeing composition is prepared:

    ______________________________________                                        1-(2,3-Diamino-5-nitrophenyl)-2-propanol                                                                 0.51   g                                           2-Butoxyethanol            10     g                                           TWEEN 80                   12     g                                           Oleic acid                 20     g                                           2-Amino-2-methyl-1-propanol at 25% strength                                                              6      g                                           in water                                                                      Water q.s.                 100    g                                           pH 6.4                                                                        ______________________________________                                    

When applied on hair for 15 minutes at 30° C., this mixture endows it,after shampooing and rinsing, with a coloration:

10 R 6/9 on hair bleached white

7.5 YR 7/4 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 11

The following dyeing composition is prepared:

    ______________________________________                                        1-(2,3-Diamino-5-nitrophenyl)-2-propanol                                                                0.4    g                                            2-Butoxyethanol           12     g                                            Carboxymethylcellulose    2      g                                            Ammonium lauryl sulphate  5      g                                            Triethanolamine in 1% strength                                                                          1.5    g                                            solution in water                                                             Water q.s.                100    g                                            pH 7.5                                                                        ______________________________________                                    

When applied on hair for 20 minutes at 30° C., this mixture endows it,after shampooing and rinsing, with a coloration:

6.25 YR 6/15 on hair bleached white

1.25 Y 8/13 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 12

The following dyeing composition is prepared:

    ______________________________________                                        1-(3-Amino-2-methylamino-5-nitrophenyl)-                                                                0.26   g                                            2-propanol                                                                    96° strength alcohol                                                                             1.0    g                                            Lauramide                 1.5    g                                            Lauric acid               1      g                                            CELLOSIZE WP 03           5      g                                            Monoethanolamine          2      g                                            Water q.s.                100    g                                            pH 9.75                                                                       ______________________________________                                    

When applied on hair for 20 minutes at 30° C., this mixture endows it,after shampooing and rinsing with a coloration:

5.5 YR 7/10 on hair bleached white

10 YR 7/6 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 13

The following dyeing composition is prepared:

    ______________________________________                                        2-(2,3-Diamino-5-nitrophenyl)ethanol                                                                     0.6    g                                           2-Methyl-4-amino-5-nitro-N--(β,γ-dihydroxy-                                                   0.17   g                                           propyl)aniline                                                                3-Nitro-4-(β-aminoethyl)amino-N,N--bis(β-                                                      0.12   g                                           hydroxyethyl)aniline dihydrochloride                                          COMPERLAN KD               2.2    g                                           Lauric acid                0.8    g                                           2-Ethoxyethanol            2      g                                           Monoethanolamine           1.2    g                                           Water q.s.                 100    g                                           pH 9                                                                          ______________________________________                                    

When applied for 15 minutes at 30° C. on hair which has been bleachedwhite, this mixture endows it, after shampooing and rinsing, with agolden chestnut coloration.

EXAMPLE 14

The following dyeing composition is prepared:

    ______________________________________                                        2-[3-Amino-2-(β-hydroxyethyl)amino-5-nitro-                                                         0.65   g                                           phenyl]ethanol                                                                3-Methylamino-4-nitrophenoxyethanol                                                                      0.2    g                                           3-Nitro-4-(β-hydroxyethyl)amino-N--methyl-                                                          0.2    g                                           aniline                                                                       2-Butoxyethanol            10     g                                           ALFOL C.sub.16/28          8      g                                           Lanette Wax E              0.5    g                                           CEMULSOL B                 1      g                                           Oleic diethanolamide       1.5    g                                           Monoethanolamine, 20% concentration by weight                                                            0.3    g                                           Water q.s.                 100    g                                           pH 9.5                                                                        ______________________________________                                    

When applied for 20 minutes at 30° C. on bleached hair, this mixtureendows it, after shampooing and rinsing, with a chestnut coloration.

EXAMPLE 15

The following dyeing composition is prepared:

    ______________________________________                                        1-(2,3-Diamino-5-nitrophenyl)-2-propanol                                                                 0.1    g                                           4-Amino-3-nitro-N--(β-hydroxyethyl)aniline                                                          0.06   g                                           4-Methylamino-3-nitro-N,N--bis(β-hydroxyethyl)-                                                     0.08   g                                           aniline                                                                       96° strength alcohol                                                                              10     g                                           CARBOPOL 934               2      g                                           5% strength ammonia solution                                                                             4      g                                           Water q.s.                 100    g                                           pH 5                                                                          ______________________________________                                    

When applied for 20 minutes at 28° C. on light chestnut-coloured hair,this mixture endows it, after shampooing and rinsing, with a goldenmedium chestnut coloration.

EXAMPLE 16

The following dyeing composition is prepared:

    ______________________________________                                        1-(3-Amino-2-methylamino-5-nitrophenyl)-2-                                                              0.08    g                                           propanol                                                                      2-(β-Hydroxyethyl)amino-4-nitrophenoxyethanol                                                      0.07    g                                           N--(4-methylamino-3-chlorophenyl)-2-methyl-5-                                                           0.06    g                                           ureidobenzoquinoneimine                                                       N--{4-[ethyl(carbamylmethyl)amino]phenyl}-2-                                                            0.052   g                                           methyl-5-ureidobenzoquinoneimine                                              96° strength alcohol                                                                             10      g                                           ALFOL C.sub.16/18         8       g                                           Lanette Wax E             0.5     g                                           CEMULSOL B                1       g                                           Oleic diethanolamide      1.5     g                                           Triethanolamine, 5% concentration by weight                                                             3       g                                           Water q.s.                100     g                                           pH 8                                                                          ______________________________________                                    

When applied for 25 minutes at 35° C. on bleached hair, this mixtureendows it, after shampooing and rinsing, with a golden medium chestnutcoloration.

EXAMPLE 17

The following dyeing mixture is prepared:

    ______________________________________                                        2-(2,3-Diamino-5-nitrophenyl)ethanol                                                                  0.33     g                                            Resorcinol              0.1      g                                            meta-Aminophenol        0.08     g                                            para-Phenylenediamine   0.08     g                                            para-Aminophenol        0.08     g                                            3-Acetamido-2,6-dimethylphenol                                                                        0.1      g                                            CEMULSOL NP 4           12       g                                            CEMULSOL NP 9           15       g                                            Polyglycerolated oleic alcohol (2 moles of                                                            1.5      g                                            glycerol                                                                      Polyglycerolated oleic alcohol (4 moles of                                                            1.5      g                                            glycerol                                                                      Propylene glycol        6        g                                            TRILON B                0.12     g                                            Ammonia solution, 22° Be                                                                       11       g                                            Mercaptosuccinic acid   0.4      g                                            Water q.s.              100      g                                            pH 9.4                                                                        ______________________________________                                    

At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28° C. on hair which is naturally 90%white, this mixture endows it, after shampooing and rinsing, with a darkblonde coloration.

EXAMPLE 18

The following dyeing mixture is prepared:

    ______________________________________                                        1-(2,3-Diamino-5-nitrophenyl)-2-propanol                                                                0.65    g                                           para-Phenylenediamine     0.21    g                                           Resorcinol                0.16    g                                           2,4-Diaminophenoxyethanol(dihydrochloride)                                                              0.075   g                                           3-(β-Hydroxyethyl)amino-6-methylphenol                                                             0.15    g                                           CELLOSIZE WP 03           2       g                                           Ammonium lauryl sulphate  5       g                                           2-Butoxyethanol           15      g                                           96° strength alcohol                                                                             5       g                                           Ammonia solution, 22° Be                                                                         10      g                                           Ammonium thiolactate      0.8     g                                           Water q.s.                100     g                                           pH 10.4                                                                       ______________________________________                                    

At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28° C. on bleached hair, this mixtureendows it, after shampooing and rinsing, with a light chestnutcoloration.

EXAMPLE 19

The following dyeing mixture is prepared:

    ______________________________________                                        1-(3-Amino-2-methylamino-5-nitrophenyl)-2-                                                             0.12    g                                            propanol monohydrochloride                                                    para-Aminophenol         0.06    g                                            4-Methylaminophenol hemisulphate                                                                       0.09    g                                            2-Methoxy-5-aminophenol  0.105   g                                            7-Hydroxybenzomorpholine 0.05    g                                            4-[Ethyl(carbamylmethyl)amino]aniline                                                                  0.1     g                                            CEMULSOL NP 4            21      g                                            CEMULSOL NP 9            24      g                                            Oleic acid               4       g                                            2-Butoxyethanol          3       g                                            96° strength ethanol                                                                            10      g                                            MASQUOL DTPA             2.5     g                                            Thioglycolic acid        0.6     g                                            Ammonia solution, 22° Be                                                                        10      g                                            Water q.s.               100     g                                            pH 10                                                                         ______________________________________                                    

At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28° C. on bleached hair, the mixtureendows it, after shampooing and rinsing, with an ashen sandy coloration.

EXAMPLE 20

The following dyeing mixture is prepared:

    ______________________________________                                        2-[3-Amino-2-(β-hydroxyethyl)amino-5-nitro-                                                       0.26    g                                            phenyl]ethanol                                                                4-[Bis(β-hydroxyethyl)amino]aniline                                                               0.19    g                                            dihydrochloride                                                               Resorcinol               0.07    g                                            4-Amino-2-chlorophenol hydrochloride                                                                   0.07    g                                            3-Carbamylmethylamino-6-methylphenol                                                                   0.1     g                                            ALFOL C 16/18            8       g                                            Lanette Wax E            0.5     g                                            CEMULSOL B               1       g                                            Oleic diethanolamide     1.5     g                                            MASQUOL DTPA             2.5     g                                            Mercaptosuccinic acid    0.5     g                                            Ammonia solution, 22° Be                                                                        11      g                                            Water q.s.               100     g                                            pH 10.4                                                                       ______________________________________                                    

At the time of use, 80 g of "20 volumes" hydrogen peroxide are added.

When applied for 25 minutes at 30° C. on hair which has been bleached toa reddish colour, the mixture endows it, after shampooing and rinsing,with a golden light brown coloration.

EXAMPLE 21

The following dyeing composition is prepared:

    ______________________________________                                        2-(2,5-Diamino-3-nitrophenyl)ethanol                                                                    0.54    g                                           2-Butoxyethanol           15      g                                           CELLOSIZE WP 03           2       g                                           (Tallow alkyl)dimethylhydroxyethylammonium                                                              2       g                                           chloride                                                                      Monoethanolamine in 20% strength aqueous                                                                1       g                                           solution                                                                      Water q.s.                                                                    pH 9.8                                                                        ______________________________________                                    

When applied on hair for 15 minutes at 30° C., this mixture endows it,after shampooing and rinsing, with a coloration:

7.5 R 5/10 on hair which has been bleached white

7.5 R 5.5/6 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 22

The following dyeing composition is prepared:

    ______________________________________                                        1-(2,5-Diamino-3-nitrophenyl)-2-propanol                                                              0.3      g                                            2-Butoxyethanol         10       g                                            96° strength alcohol                                                                           5        g                                            CELLOSIZE WP 03         2        g                                            Ammonium lauryl sulphate                                                                              5        g                                            Water q.s.              100      g                                            pH 6.9                                                                        ______________________________________                                    

When applied on hair for 20 minutes at 28° C., this mixture endows it,after shampooing and rinsing, with a coloration:

8 R 5/10 on hair which has been bleached white

7.5 R 5.5/6 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 23

The following dyeing composition is prepared:

    ______________________________________                                        1-[2-Amino-5-(β-hydroxyethyl)amino-3-                                                           0.7       g                                            nitrophenyl]-2-propanol                                                       96° strength alcohol                                                                          10        g                                            ALFOL C.sub.16/18      8         g                                            Lanette Wax E          0.5       g                                            CEMULSOL B             1         g                                            Oleic diethanolamide   1.5       g                                            5% strength ammonia solution q.s. pH 9.9                                      Water q.s.             100       g                                            ______________________________________                                    

When applied on hair for 10 minutes at 28° C., this mixture endows it,after shampooing and rinsing, with a coloration:

7.5 RP 4/9 on hair which has been bleached white

7.5 RP 5.5/4 on hair which is naturally 90% white, these colours beingexpressed according to Munsell's notation.

EXAMPLE 24

The following dyeing composition is prepared:

    ______________________________________                                        1-(2,5-Diamino-3-nitrophenyl)-2-propanol                                                               0.16    g                                            2-Amino-3-nitrotoluene   0.095   g                                            3-Nitro-4-[(γ-hydroxypropyl)amino]aniline                                                        0.12    g                                            1,4,5,8-Tetraaminoanthraquinone                                                                        0.12    g                                            (Cibacete microdisperse sapphire blue)                                        LAURAMIDE                1.5     g                                            Lauric acid              1       g                                            CELLOSIZE WP 03          5       g                                            Monoethanolamine         2       g                                            Water q.s.               100     g                                            pH 9.5                                                                        ______________________________________                                    

When applied for 20 minutes at 28° C. on hair which is naturally 90%white, this mixture endows it, after shampooing and rinsing, with acoppery blonde coloration.

EXAMPLE 25

The following dyeing composition is prepared:

    ______________________________________                                        2-(2,5-Diamino-3-nitrophenyl)ethanol                                                                    0.2     g                                           2-Amino-3-nitrophenol     0.15    g                                           3-Nitro-4-methylamino-N--(β-aminoethyl)aniline                                                     0.08    g                                           hydrobromide                                                                  96° strength alcohol                                                                             10      g                                           LAURAMIDE                 1.5     g                                           Lauric acid               1       g                                           CELLOSIZE WP 03           5       g                                           Monoethanolamine          2       g                                           Water q.s.                100     g                                           pH 9.7                                                                        ______________________________________                                    

When applied for 25 minutes at 28° C. on hair which has been bleachedwhite, this mixture endows it, after shampooing and rinsing, with areddish-copper coloration.

EXAMPLE 26

The following dyeing composition is prepared:

    ______________________________________                                        1-[2-Amino-5-(β-hydroxyethyl)amino-3-nitro-                                                        0.36    g                                           phenyl]-2-propanol                                                            3-Nitro-4-aminophenol     0.13    g                                           2-(β-Hydroxyethyl)amino-5-{4-[bis(β-hydroxy-                                                  0.17    g                                           ethyl)amino]anilino}-1,4-benzoquinone                                         96° strength alcohol                                                                             20      g                                           CELLOSIZE WP 03           2       g                                           (Tallow alkyl)dimethylhydroxyethylammonium                                                              2       g                                           chloride                                                                      Triethanolamine, 5% concentration                                                                       0.2     g                                           Water q.s.                100     g                                           pH 7.7                                                                        ______________________________________                                    

When applied for 20 minutes at 28° C. on hair which is naturally 90%white, this mixture endows it, after shampooing and rinsing, with acoppery blonde coloration.

EXAMPLE 27

    ______________________________________                                        1-(2,5-Diamino-3-nitrophenyl)-2-propanol                                                               0.7     g                                            1-[2-Amino-5-(β-hydroxyethyl)amino-3-nitro-                                                       0.06    g                                            phenyl]-2-propanol                                                            2,5-Diaminopyridine dihydrochloride                                                                    0.05    g                                            para-Aminophenol         0.08    g                                            α-Naphthol         0.035   g                                            7-Hydroxybenzomorpholine 0.07    g                                            1-(2,4-Diaminophenoxy)-2,3-propanediol                                                                 0.04    g                                            hydrochloride                                                                 N--(β-Methoxyethyl)-para-phenylenediamine                                                         0.04    g                                            dihydrochloride                                                               Polyglycerolated oleic alcohol (2 moles of                                                             4.5     g                                            glycerol)                                                                     Polyglycerolated oleic alcohol (4 moles of                                                             4.5     g                                            glycerol)                                                                     ETHOMEEN TO 12           4.5     g                                            COMPERLAN KD             9       g                                            Propylene glycol         4       g                                            2-Butoxyethanol          8       g                                            96% o strength ethanol   6       g                                            MASQUOL DTPA             2       g                                            Hydroquinone             0.15    g                                            Sodium bisulphite solution, 35° Be                                                              1.3     g                                            Ammonia solution, 22° Be                                                                        10      g                                            Water q.s.               100     g                                            pH 10.5                                                                       ______________________________________                                    

At this time of use, 110 g of "20 volumes" hydrogen peroxide are added.

When applied for 20 minutes at 28° C. on hair which is naturally 90%white, the mixture endows it, after shampooing and rinsing, with an ashblonde coloration.

EXAMPLE 28

The following dyeing mixture is prepared:

    ______________________________________                                        1-[2-Amino-5-(β-hydroxyethyl)amino-3-nitro-                                                         0.1    g                                           phenyl]-2-propanol                                                            2-[2-(β-hydroxyethyl)amino-3,5-dinitrophenyl]-                                                      0.8    g                                           ethanol                                                                       2-Methylresorcinol         0.06   g                                           para-Phenylenediamine      0.05   g                                           2,4-Diaminophenoxyethanol dihydrochloride                                                                0.03   g                                           CEMULSOL NP 4              21     g                                           CEMULSOL NP 9              24     g                                           Oleic acid                 4      g                                           2-Butoxyethanol            3      g                                           96° strength ethanol                                                                              10     g                                           MASQUOL DTPA               2.5    g                                           Sodium bisulphite solution, 35° Be                                                                1      g                                           Ammonia solution, 22° Be                                                                          10     g                                           Water q.s.                 100    g                                           pH 10.6                                                                       ______________________________________                                    

At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 30 minutes at 28° C. on bleached hair, the mixtureendows it, after shampooing and rinsing, with a bluish-grey coloration.

EXAMPLE 29

The following dyeing mixture is prepared:

    ______________________________________                                        2-(2,5-Diamino-3-nitrophenyl)ethanol                                                                    0.08    g                                           2-[2-(β-hydroxyethyl)amino-3,5-dinitro-                                                            0.07    g                                           phenyl]ethanol                                                                para-Phenylenediamine     0.06    g                                           Resorcinol                0.035   g                                           5-Acetamido-2-methylphenol                                                                              0.09    g                                           1-Phenyl-3-methyl-5-pyrazolone                                                                          0.065   g                                           CARBOPOL 934              3       g                                           96° strength alcohol                                                                             11      g                                           2-Butoxyethanol           5       g                                           (Tallow alkyl)dimethylhydroxyethylammonium                                                              2       g                                           chloride                                                                      TRILON B                  0.2     g                                           Ammonia solution, 22° Be                                                                         10      g                                           Sodium bisulphite, 35° Be                                                                        1       g                                           Water q.s.                100     g                                           pH 10.2                                                                       ______________________________________                                    

At the time of use, 100 g of "20 volumes" hydrogen peroxide are added.

When applied for 20 minutes at 28° C. on hair which is naturally 90%white, the mixture endows it, after shampooing and rinsing, with apinkish dark blonde coloration.

EXAMPLE 30

The following dyeing mixture is prepared:

    ______________________________________                                        1-[2-Amino-5-(β-hydroxyethyl)amino-3-                                                               0.08   g                                           nitrophenyl]-2-propanol                                                       para-Aminophenol           0.09   g                                           1,4-Diamino-2,6-dimethylbenzene dihydrochloride                                                          0.04   g                                           Resorcinol                 0.06   g                                           [2-Amino-4-(β-hydroxyethyl)aminophenoxy]-                                                           0.05   g                                           ethanol dihydrochloride                                                       CELLOSIZE WP 03            2      g                                           Ammonium lauryl sulphate   5      g                                           2-Butoxyethanol            15     g                                           96° strength alcohol                                                                              5      g                                           Ammonia solution, 22° Be                                                                          10     g                                           Ammonium thiolactate       0.8    g                                           Water q.s                  100    g                                           pH 10.1                                                                       ______________________________________                                    

At the time of use, 120 g of "20 volumes" hydrogen peroxide are added.

When applied for 40 minutes at 30° C. on hair which is naturally 90%white, the mixture endows it, after shampooing and rinsing with a pearlylight grey coloration.

The various trade names used in the above examples are clarified ingreater detail below:

ALFOL C_(16/18) : cetyl/stearyl alcohol sold by Condeea.

Lanette Wax E: partially sulphated cetyl/stearyl alcohol, sold byHenkel.

CEMULSOL B: ethoxylated castor oil, sold by Rhone-Poulenc.

CELLOSIZE WP 03: hydroxyethylcellulose, sold by UNION CARBIDE

LAURAMIDE: lauric acid monoethanolamide, sold by Witco.

ETHOMEEN TO 12: oxyethylenated oleylamine (12 moles of ethylene oxide),sold by ARMAK.

COMPERLAN KD: coconut fatty acid diethanolamide, sold by HENKEL.

MASQUOL DTPA: diethylenetriaminepentaacetic acid pentasodium salt, soldby PROTEX.

CEMULSOL NP 4: oxyethylenated nonylphenol (4 moles of ethylene oxide),sold by Rhone-Poulenc.

CEMULSOL NP 9: oxyethylenated nonylphenol (9 moles of ethylene oxide)sold by Rhone-Poulenc.

CARBOPOL 934: acrylic acid polymer of M.W. 2 to 3 million, sold byGOODRICH CHEMICAL COMPANY.

TRILON B: ethylenediamine tetraacetic acid.

TWEEN 80: polyoxyethylenated sorbitol mono-oleate.

We claim:
 1. Compound of formula (I) below: ##STR21## in which: Xdenotes a branched or unbranched alkylene radical containing 2 to 6carbon atoms, unsubstituted or substituted with one or more hydroxylradicals;R denotes a hydrogen, an alkyl or a mono- or polyhydroxyalkylradical or an aminoalkyl radical in which the amine group can be mono-or disubstituted with an alkyl radical or with a mono- orpolyhydroxyalkyl radical, and the alkyl radicals containing 1 to 4carbon atoms; R' denotes a hydrogen atom or a C₁ to C₄ alkyl radical; Yand Z denote a nitro and/or --NHR₁ radical, R₁ and R, may be identicalor different, R₁ having the meanings given above for R, with the provisothat when they are identical to each other, Y and Z both denote nitroradicals, and the cosmetically acceptable salts of the compoundscontaining a salifiable amine group. 2.2,4-Dinitro-6-hydroxyalkylaniline of formula (I) according to claim 1 inwhich Y and Z denote a nitro radical, having the formula: ##STR22## inwhich R', X or R have the meanings given above, and the cosmeticallyacceptable salts of the compounds containing a salifiable amine group.3. Compound according to claim 1, in which R' is hydrogen or a methylradical, X is chosen from the group consisting of ethylene, propylene,1,1-dimethylethylene, 1,2-dimethylethylene and 1,1,2-trimethylethyleneradicals and R is chosen from the group consisting of hydrogen andmethyl, ethyl, n-propyl, β-hydroxyethyl, γ-hydroxypropyl,β,γ-dihydroxypropyl, β-aminoethyl and β-diethylaminoethyl radicals. 4.2-Amino-4-nitro-6-hydroxyalkylaniline of formula (I) according to claim1 in which Z denotes a nitro radical and Y an --NHR₁ radical, having theformula ##STR23## in which R', X, R and R₁ have the meanings given inclaim 1, or the cosmetically acceptable salts of the compoundscontaining a salifiable amine group.
 5. Compound according to claim 4,in which R', in which R' is hydrogen or a methyl radical, X is chosenfrom the group consisting of ethylene, propylene, 1,1-dimethylethylene,1,2-dimethylethylene or 1,1,2-trimethylethylene radicals and R and R₁are chosen from the group consisting of hydrogen and methyl, ethyl,n-propyl, β-hydroxyethyl, γ-hydroxypropyl, β,γ-dihydroxypropyl,β-aminoethyl and β-diethylaminoethyl radicals. 6.2-Nitro-4-amino-6-hydroxyalkylaniline of formula (I) according to claim1 in which Y denotes a nitro radical and Z and --NHR₁ radical, havingthe formula ##STR24## in which R', X, R and R₁ have the meanings givenin claim 1, or the cosmetically acceptable salts of the compoundscontaining a salifiable amine group.
 7. Compound according to claim 6,in which R' is hydrogen or a methyl radical, X is chosen from the groupconsisting of ethylene, propylene, 1,1-dimethylethylene,1,2-dimethylethylene and 1,1,2-trimethylethylene radicals and R and R₁are chosen from the group consisting of hydrogen and methyl, ethyl,n-propyl, β-hydroxyethyl, γ-hydroxypropyl, β,γ-dihydroxypropyl,β-aminoethyl and β-diethylaminoethyl radicals.
 8. Compound according toclaim 2, chosen from the group consisting of:2-(2-amino-3,5-dinitrophenyl)ethanol,2-[2-(β-hydroxyethyl)amino-3,5-dinitrophenyl]ethanol,1-(2-amino-3,5-dinitrophenyl)-2-propanol,1-(2-methylamino-3,5-dinitrophenyl)-2-propanol,1-[2-(β-aminoethyl)amino-3,5-dinitrophenyl]-2-propanol or the salts ofthese compounds.
 9. Compound according to claim 4, chosen from the groupconsisting of: 2-(2,3-diamino-5-nitrophenyl)ethanol,2-[3-amino-2-(β-hydroxyethyl)amino-5-nitrophenyl]ethanol,1-(2,3-diamino-5-nitrophenyl)-2-propanol, and1-(3-amino-2-methylamino-5-nitrophenyl)-2-propanol or the salts of thesecompounds.
 10. Compound according to claim 6, chosen from the groupconsisting of: 2-(2,5-diamino-3-nitrophenyl)ethanol,1-(2,5-diamino-3-nitrophenyl)-2-propanol, and1-[2-amino-5-(β-hydroxyethyl)amino-3-nitrophenyl]-2-propanol or thesalts of these compounds.
 11. Dyeing composition for human hair, whichcontains at least one compound as defined in claim 1 in a solventmedium.
 12. Composition according to claim 11, which contains 0.0001 to5% by weight of at least one compound of formula (I), relative to thetotal weight of the composition.
 13. Composition according to claim 11,which has a pH of between 3 and 11.5.
 14. Composition according to claim11, in which the solvents are chosen from the group consisting of water,lower alkanols, aromatic alcohols, polyols, glycols or glycol ethers,and mixtures thereof.
 15. Composition according to claim 11, whichcontains, in addition, cosmetic adjuvants chosen from the groupconsisting of anionic, cationic, nonionic or amphoteric surfactants ormixtures thereof, thickeners, dispersants, penetrants, sequesteringagents, film-forming agents, buffers, perfumes and alkalinising oracidifying agents.
 16. Composition according to claim 11, intended foruse for direct dyeing of human hair, which contains, in addition, otherdirect dyes chosen from the group consisting of azo dyes, anthraquinonedyes, indophenols, indoanilines and nitro derivatives of the benzeneseries other than those of formula (I).
 17. Composition according toclaim 11, intended for use as a hair setting lotion, which takes theform of an aqueous, alcoholic or hydroalcoholic solution containing atleast one cosmetic resin.
 18. Composition according to claim 11,intended for use for oxidation dyeing, which contains in addition atleast one oxidation dye precursor.
 19. Composition according to claim18, which has a pH of between 7 and 11.5, and which contains, inaddition, a reducing agent.
 20. Process for dyeing human hair, whichconsists in applying a composition as defined in claim 11 on the fibres,in leaving the composition in place for 5 to 50 minutes, and thenrinsing the fibres, optionally washing them, rinsing again and dryingthem.
 21. Process for dyeing human hair, which consists in applying acomposition as defined in claim 17 on the fibres which have been washedand rinsed, optionally coiling the fibres and drying them.
 22. Processfor dyeing human hair, which consists in applying on the fibres acomposition as defined in claim 18, to which an oxidising agent isoptionally added, in leaving the composition in place for 10 to 50minutes, and in rinsing the fibres, optionally washing them withshampoo, rinsing again and drying them.
 23. Composition according toclaim 15, which contains 0.05 to 2%, by weight of at least one compoundof formula (I), relative to the total weight of the composition.